Cationic monoazo dyes for acrylic and polyester fibers



dye compounds having the general formula Mario Francesco Sartori,Wilmington, Del, assignor to E. E. du Pont de Nemours and Company,Wilmington,

AND

DeL, a corporation of Delaware No Drawing. Filed Nov. 30, 1959, Ser. No.855,967

, v 3 Claims. (Cl. 260-158) This invention relates tonovel-water-soluble, organic compounds which are useful as dyes foracid-modified acrylic polyester fibers. modified acrylic fiber,throughout this specification and claims, I mean acrylic fiber havingacid sites; for instance, the sulfonate modified acrylic fibersdescribed in U.S.P. 2,837,500 and 2,837,501. By acid-modiiied polyesterfiber, I mean polyethylene terephthalate fiber containingmetal-sulfonate groups, as described more fully in Belgian Patent No.549,179, granted July 14, 1957.

It is an object of this invention to provide novel cationic azo dyesuseful for dyeing the aforementioned fibers, producing thereon reddyeings of outstanding brightness and good light fastness, and which arefurthermore character-- ized by stability of the shade over a wide rangeof pH variations, particularly in the region from pH 3 to pH 9.5. By thelatter mentioned stability I mean that the shade of the dyeing on theaforementioned fibers does not change perceptibly with change of H-ionconcentration in the pH range indicated. Other objects and achievementsof this invention will become apparent as the description proceeds. g

Now, according to my invention, the above objects are satisfactorilyachieved by a group of novel cationicazo 'or OCH Y designates H, Cl, CHC l-l or OCH R By acrylic fiber or acidthen stirred at this temperaturefor two hours. An excess of nitrous acid is maintained during this timeand is then removed by the addition of small amounts of urea.

This diazo solution is then added during about one half hour. to astirred solution of 48.6 parts (0.2 mole)" of[.2-(N-ethylanilino)ethyl]trimethylammonium chloride in 100 parts ofwater, while keeping the temperature at 0 to 2 C. After stirring for onehour at this temperature sodium acetate is added to bring the pH to 4-5and the agitationis continued at 2 to 5 C. for an additional ten hours.The reaction mixture is then stirred at room temperature for 8 hours.Sodium chloride is added and the red dye, which precipitates, isfiltered oif, washed with 20% sodium chloride solution and dried. Thenew dye' has the formula v v nor- N Y 5-, elm cmsoz-ii il-N=N-ON g s I Ic HroHr-iuomn," o1- t is a violet-red powder, which dissolves in water.to give a red'solution. -The1absorption maximum in ethanol is located at502 millimicrons. It dyes acid-modified po1y-.

acrylic fibers and acid-modified polyester fibers bright red shades ofgood fastness properties.

When the [2-N-ethylanilino)ethyl]trimethylammonium chloride ofthisexample is replaced with an equivalent amount of[Z-(N-ethyl-m-toluidino)ethyl]trimethylammonium chloride, a dye ofhomologous formula and similar dyeing properties is obtained.

7 Example 2 .to 100 parts of sulfuric acid monohydrate. Powdered2-amino-5methylsulfonylthiazole 35.6 parts) is then added portionwise at5 C. and the obtained slurry is stirred at 5 C. for an additional 3hours. An excess of stands for hydrogen, Z-hydroxyethyl, Z-cyanoethyl orlower alkyl; R R and R designate radicals of the groupconsisting oflower alkyl, benzyl and Z-hydroxyethyl; and A is a water-solubilizinganion, for instance chloride,

bromide, alkyl sulfate, p-toluenesulfonate, etc.

Example 1 Nitrosylsulfuric acid is prepared by adding portionwise 14.5parts (0.2 1 mole) of sodium nitrite, finely ground, to 100 parts of 96%sulfuric acid while stirring and keeping the temperature between 25 andC. Stirring is continued until a clear solution is formed. To thissolution, cooled to 5 C., is added dropwise, a mixture of 340 parts ofacetic acid and 60 parts of propionic acid, while stirring and allowingthe temperature to rise to 15 C. The mixture is then cooled to between 2C. and +2 C., and a solution of 35.6 parts (0.2 mole) of2-amino-5-methylsulfonylthiazole (J. Org. Chem. 24, 194), in a mixtureof 340 parts of acetic acid and 60 parts of propionic acid, is addedportionwise, while keepsodium nitrite is maintained during this tiine'and is then removed by the addition of small amounts of urea. This diazosolution is then added during about one half'hour to a stirred solutioncontaining 70.4 parts of [2-(o-chloroanilino)ethyl]diethylmethylammoniummethosulfate in parts of water, while keeping the temperature at 0 to 2C. After stirring one hour at this temperature, sodium acetate is addedto reduce the acidity to pH 4, and the agitation is continued at 2 C. to5 C. for an additional 10 hours.

The obtained dye is then salted out, filtered ofi, washed with 20%sodium chloride solution and dried. The new dye has the formula:

It is a scarlet powder, which is soluble in water, giving a redsolution. The absorption maximum in ethanol is located at 488millimicrons. It dyes'acid modified acrylic Example 3 v A diazotizedsolution of 3.5 parts of Z-amino-S-methylsulfonylthiazole, prepared bythe procedure described in Example 1, is added during about one halfhour to a stirred solution of 7.2 parts ofdiethylmethyl[2-(5-methyl-o-anisidino)ethyl] ammonium methosulfate in 10parts Patented May 8, 1862" oi water, while keeping the temperature atC. to 2 6.: The'formedjdy'e, isolated as describedinExample 1, has

' i the formula.

don, 1 i (3.235

CH3 I V It dyes acid modified-acrylic-fibers violet-red shades of goodfastness properties. 1

Example 4 following the procedure of EXarnple 1, and employingthe diazoand coupling components shown in the following table, basic-red fibersare obtained.

dyes for; acid modified acrylic .DlazoComponent I (a) ammo--ethylsulfonylrm 1e azo H (b) 2-amino -5-n-butylsulionylthiazole. I

I (c) z-aniinoen prppylsulfonyb thia-zole.

(e) 2-an1ino-5-methylsn1fony1- .thiazo e. (j)2-amino-5methylsullonylthiazole. r

(h) z-a'gninoefmethylsultonylthiazole -2 muslinemtut rsunonyr;

tlnazole.

I a Coupling Component [2- (N-methyl -3-ethylanilino) -e th yl] trimethylammonium chloride;

{2 (N n-butyl manisidino) -ethyl1triethylamrnonium chloride.

'n-butyldime th y1[2- (N -n-propyl-2,5-

diohloroanilino) -ethyl] ammonium ylanilinmethyll-trimethylammoniumchlorid benzyl 1m chloride. r 1 [2 (N-2-hydroxyethyl-2-chloro 5 methe.dimethyliZ: N-2-cyanoethylani- 7 guns methods.

Cal

part of a non-ionic dispersing agent (for instance, the condensationproduct of oleyl alcohol with moles of eth ylene oxide) The fabric isrinsed and then boiled for 2 hours; in a dye bath consisting of l part,of glacial acetic, 1 part'of the dye produced in Example 1, 0.3'part ofsodium acetate and 4000 parts of water; The fabric is then 'rinsed'inwarm water and scoured as before. Finally, the fabric is rinsed, driedand pressed.

It will he understood that the details of the above examples may bevaried widely within the skill of those engaged in this art.

The novel compounds of this invention not only satisfy the aboveenumerated principal objects of this invention,

The Z-amin -S-methyIsuIfoByl and I S-n-butylsulfbhyl- 'thiaizoles andtheir preparation are described in J1 Org. Chenn, Vol.24, at pages 193and 194; Theethylsulfonyl and 'propylsulfonyl homolog may be'preparedfby analo- The coupling components are either known compounds. or may beprepared by known methods. For instance, the coupling component firstnamed in Example; .1 may be prepared by'reac'ting NethyKN-fi-hydroxyethyl)aniline with phosphorus oxychlorideto producethecorresponding N-o-chloroethyl compound, and then reacting the latterwith trimethyl-- amine toproduce the quaternary compound. The componentfirst named in Example ,2 may be prepared byalkylating the diamine offormula 01 Genome by one or :the other of the above procedures dependingon whether their anionic member is Cl or the methosulfate-radical, V

The following example will illustrate a practical dyeingprocedurejforuse with my novel colors.

named in the above examples 1 but! find that they also possess goodgeneral fastness qualities (e.g. washing, soaping, etc.) andtheyexhibit' thea ro perty of good buildup on tone to providetdeep'shades of red;

In the'claims below, the term .lower alkyl shall be v understood asdefining an alltyl radical of 1 to 4 C-atorns. I claim as myinvention: 1. A cationic azo dye of the formula I v p X I Y wherein R isan alkyl radical of 1 to 4 C-atoms; X is a member of the groupconsisting of H, Cl and OCH Y is a member of the group consisting ofI-LCl, CH C 11 'and QCH RylS a member of the group consisting of hy-"dro'g'en, Z-hydroxyethyl, 2acyanoethyl 'and lower alkyl;

R R and R are members selected from the group consisting of lower alkyl,benzyl and Z-hydroxyethyl; and A- is a water-solubilizing anion. a

V 2 The azo dye of formula ii a "cursors C-NNONQHQ m-fiwnm,o1-

3. v The azo dye of formula 7 CH3 References Cited in the tile of thispatent UNITED STATES PATENTS 2,864,812 7 Bossard er al. r Dec. 16, 1952,889,315 Bossard et a1. June 2, 1959 2,893,816 Tsang et al. July 7,19592,972,508 Kruckenberget a1. Feb. 21, 1961 V FOREIGN PATENTS 1 477,913Germany .--May 30, 1929' 501,623 Germany lune 19, 1930 556,218 CanadaApr. 22, 1958 OTHER REFERENCES 'Dickey et a1.: L Org. Chem, vol. 24, pp.187496, February 1959. (Copy in Patent Oifice Science Library.)

1. A CATIONIC AZO DYE OF THE FORMULA